EP0496221A2 - Ionenleiter aus Fluoriden - Google Patents

Ionenleiter aus Fluoriden Download PDF

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Publication number
EP0496221A2
EP0496221A2 EP92100342A EP92100342A EP0496221A2 EP 0496221 A2 EP0496221 A2 EP 0496221A2 EP 92100342 A EP92100342 A EP 92100342A EP 92100342 A EP92100342 A EP 92100342A EP 0496221 A2 EP0496221 A2 EP 0496221A2
Authority
EP
European Patent Office
Prior art keywords
electric conductivity
temperature
ionic conductor
fluoride
ionic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP92100342A
Other languages
English (en)
French (fr)
Other versions
EP0496221A3 (en
Inventor
Kazunori Takada
Shigeo Kondo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP0496221A2 publication Critical patent/EP0496221A2/de
Publication of EP0496221A3 publication Critical patent/EP0496221A3/en
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/182—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte
    • H01M6/183—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte with fluoride as solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a solid electrolyte used for a cell, a sensor such as an ionic sensor and an electrochemical display element and the like and more particularly to an ionic conductor in which fluoride ions conduct.
  • a fluoride ionic conductor such as ⁇ -PbF2, CaF2, LaF2, and the like have been generally known.
  • the electrolytic conductivity (the ionic conductivity) of these materials is about 10 ⁇ 6 S/cm at room temperature.
  • PbSnF4 has a high ionic conductivity of 10 ⁇ 3 S/cm.
  • a cell, an ionic sensor and the like are suggested as elements using these fluoride ionic conductors.
  • an excellent ionic conductivity at room temperature is particularly desirable, because when an electrochemical element such as a cell, a sensor, an electrochemical display element and the like is made of the solid electrolyte, the ionic conductivity is related with the inside impedance of the element:
  • the excellent ionic conductivity of the solid electrolyte makes the inside impedance of the electrochemical element formed thereby low.
  • poor ionic conductivity makes the inside impedance high, resulting in deteriorating discharge efficiency in a cell, and slowing speed of response in a sensor and an electrochemical display element. Therefore, the ionic conductivity of the solid electrolyte needs to be improved at room temperature.
  • the present invention provides a fluoride ionic conductor with improved ionic conductivity.
  • the ionic conductor used for a solid electrolyte of this invention which overcomes the above-discussed and numerous other disadvantages and deficiencies of the prior art, comprises fluorine, an element of the fourth group of the periodic table and zirconium.
  • the element of the fourth group of the periodic table is lead or tin.
  • the ionic conductor is Pb 1-x Sn 1-y Zr x+y F 4+2x+2y wherein 0 ⁇ x+y ⁇ 0.16.
  • the ionic conductor is Pb 1-x Sn 1-y Zr x+y F 4+2x+2y wherein 0 ⁇ x+y ⁇ 0.02.
  • the ionic conductor has a fluorite crystal structure.
  • the fluorine is in the form of an anion
  • the zirconium and the element are in the form of a cation.
  • an ionic conductor used for a solid electrolyte comprises fluorine, zirconium and an element, which belongs to the second group in the periodic table.
  • the ionic conductor has a fluorite crystal structure.
  • the fluorine is in the form of an anion
  • the zirconium and the element are in the form of a cation.
  • the invention described herein makes possible the objectives of providing (1) a fluoride ionic conductor used for a solid electrolyte with a high conductivity, (2) an ionic conductor used for a solid electrolyte comprising fluorine, zirconium and an element of the fourth group of the periodic table, (3) an ionic conductor used for a solid electrolyte comprising fluorine, lead and tin, (4) an ionic conductor used for a solid electrolyte with a composition of Pb 1-x Sn 1-y Zr x+y F 4+2x+2y (wherein 0 ⁇ x+y ⁇ 0.16) and (5) an ionic conductor used for a solid electrolyte comprising fluorine, zirconium and an element of the second group of the periodic table.
  • a fluoride ionic conductor with a composition of Pb 1-x Sn 1-x Zr 2x F 4+4x (wherein 0 ⁇ x ⁇ 0.08), which is the composition of Pb 1-x Sn 1-y Zr x+y F 4+2x+2y (wherein 0 ⁇ x+y ⁇ 0.16) when x y, is obtained as follows:
  • PbF2 Lead fluoride
  • SnF2 and ZrF2 are weighed so as to make the molar ratio 1-x:1-x:2x, then crushed and mixed with an agate mortar (the average particle diameter: 50 ⁇ m).
  • the crushed powder is pelletized with a diameter of 10 mm, a thickness of 3 mm and a powder density of 4.7 g/cm3 by a compression molding machine (temperature: room temperature, pressing time: 10 sec.).
  • the pellet is put in a reaction tube of nickel, the air in which has been exchanged for argon. Then hydrogen fluoride and argon as carrier gas are made to flow through the tube at a flow rate of 20 ml/min., and the tube is heated at 350°C for six hours, thereby obtaining a sintered sample.
  • a fluoride ionic conductor with a composition of PbSnF4 is obtained.
  • the same procedure as above is repeated to obtain a sintered sample except for using PbF2 and SnF2 with a 1:1 molar ratio.
  • the ionic conductivity is higher than that of the conventional fluoride ionic conductor, PbSnF4 with the electric conductivity of 3.2x10 ⁇ 2 S/cm.
  • Figure 2 shows the relationship between the inverse of the absolute temperature and the electric conductivity (an Arrhenius plot) at each zirconium ion concentration (x).
  • x zirconium ion concentration
  • the electric conductivity is 5.0x10 ⁇ 1 S/cm.
  • the electric conductivity is 5.0x10 ⁇ 1 S/cm.
  • the electric conductivity in the high temperature area is found to be improved compared with that of a conventional fluoride ionic conductor, PbSnF4 with an electric conductivity of 5.0x10 ⁇ 1 S/cm at 400°C.
  • the first example of the present invention can provide a fluoride ionic conductor with a higher ionic conductivity.
  • PbF2 Lead fluoride
  • SnF2 and ZrF2 are weighed so as to make the molar ratio 0.99:1-y:0.01+y, then crushed and mixed with an agate mortar (the average particle diameter: 50 ⁇ m).
  • the crushed powder is molded into pellets with a diameter of 10 mm, a thickness of 3 mm and a powder density of 4.7 g/cm3 by a compression molding machine (temperature: room temperature, pressing time: 10 sec.).
  • the pellet is put in a reaction tube of nickel, the air in which has been exchanged for argon. Then hydrogen fluoride and argon as carrier gas are made to flow through the tube at a flow rate of 20 ml/min., and the tube is heated at 350°C for six hours, thereby obtaining a sintered sample.
  • a fluoride ionic conductor with a composition of PbSnF4 is obtained.
  • the same procedure as above is repeated to obtain a sintered sample except for using PbF2 and SnF2 with a 1:1 molar ratio.
  • the ionic conductivity is higher than that of a conventional fluoride ionic conductor, PbSnF4 with an electric conductivity of 3.2x10 ⁇ 2 S/cm.
  • the second example of the present invention can provide a fluoride ionic conductor with a higher ionic conductivity.
  • a fluoride ionic conductor with a composition of Pb 1-x Sn 0.99 Zr x+0.01 F 4.02+2x (wherein 0 ⁇ y ⁇ 0.18), which is the composition of Pb 1-x Sn 1-y Zr x+y F 4+2x+2y (wherein 0.01 ⁇ x+y ⁇ 0.19) when y 0.01, is obtained as follows: Lead fluoride (PbF2), tin fluoride (SnF2) and zirconium fluoride (ZrF2) are used to make a sample.
  • PbF2 Lead fluoride
  • SnF2 tin fluoride
  • ZrF2 zirconium fluoride
  • PbF2, SnF2 and ZrF2 are weighed so as to make the molar ratio 1-x:0.99:x+0.01, then crushed and mixed with an agate mortar (the average particle diameter: 50 ⁇ m).
  • the crushed powder is molded into pellets with a diameter of 10 mm, a thickness of 3 mm and a powder density of 4.7 g/cm3 by a compression molding machine (temperature: room temperature, pressing time: 10 sec.).
  • the pellet is put in a reaction tube of nickel, the air in which has been exchanged for argon. Then hydrogen fluoride and argon as carrier gas are made to flow through the tube at a flow rate of 20 ml/min., and the tube is heated at 350°C for six hours, thereby obtaining a sintered sample.
  • a fluoride ionic conductor with a composition of PbSnF4 is obtained.
  • the same procedure as above is repeated to obtain a sintered sample except for using PbF2 and SnF2 with a 1:1 molar ratio.
  • the ionic conductivity is higher than that of a conventional fluoride ionic conductor, PbSnF4 with an electric conductivity of 3.2x10 ⁇ 2 S/cm.
  • the third example of the present invention can provide a fluoride ionic conductor with a higher ionic conductivity.
  • the ionic conductor of the present invention is a crystal with a fluorite structure having an element of the fourth group of the periodic table as a cation and fluorine as an anion.
  • the zirconium ion exists in the crystal as a tetravalent cation. Therefore, the fluoride ions become excessive in the crystal lattice. These excessive fluoride ions contribute to the ionic conduction as interstitial ions.
  • the ionic conductor of the present invention has a high conductivity.
  • an ionic conductor including an element of the fourth group of the periodic table, fluorine and zirconium is described. Furthermore, an ionic conductor including an element of the second group of the periodic table, such as Ca, fluorine and zirconium can obtain the same effect.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Conductive Materials (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)
EP19920100342 1991-01-14 1992-01-10 Fluoride ionic conductor Withdrawn EP0496221A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2636/91 1991-01-14
JP3002636A JPH04238815A (ja) 1991-01-14 1991-01-14 フッ化物イオン伝導体およびそれを用いた電気化学素子

Publications (2)

Publication Number Publication Date
EP0496221A2 true EP0496221A2 (de) 1992-07-29
EP0496221A3 EP0496221A3 (en) 1992-09-09

Family

ID=11534873

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920100342 Withdrawn EP0496221A3 (en) 1991-01-14 1992-01-10 Fluoride ionic conductor

Country Status (4)

Country Link
US (1) US5320917A (de)
EP (1) EP0496221A3 (de)
JP (1) JPH04238815A (de)
CA (1) CA2058875A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3722106B2 (ja) 2002-10-01 2005-11-30 株式会社豊田中央研究所 二次電池
RU2295178C2 (ru) * 2005-04-21 2007-03-10 Общество с ограниченной ответственностью "Высокоэнергетические батарейные системы" (ООО "ВЭБС") Твердотельный вторичный источник тока
JP6377924B2 (ja) * 2014-03-14 2018-08-22 積水化学工業株式会社 ハロゲン二次電池
JP6702142B2 (ja) * 2016-11-02 2020-05-27 トヨタ自動車株式会社 フッ化物イオン電池
KR102075607B1 (ko) * 2017-06-01 2020-02-10 도요타 지도샤（주） 정극 활물질 및 불화물 이온 전지
EP3676897A1 (de) * 2017-09-01 2020-07-08 Ambercon Technology (UK) Limited Verfahren zur herstellung eines nanopartikelmaterials und fluoridionenbatterie
JP6863212B2 (ja) * 2017-10-05 2021-04-21 トヨタ自動車株式会社 固体電解質
JP6852653B2 (ja) * 2017-11-07 2021-03-31 トヨタ自動車株式会社 正極活物質およびフッ化物イオン電池
JP6943219B2 (ja) * 2018-04-27 2021-09-29 トヨタ自動車株式会社 フッ化物イオン電池
JP6947119B2 (ja) 2018-05-14 2021-10-13 トヨタ自動車株式会社 正極活物質およびフッ化物イオン電池
JP7616890B2 (ja) 2021-01-26 2025-01-17 本田技研工業株式会社 フッ化物イオン二次電池用負極及びこれを備えるフッ化物イオン二次電池

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266867A (en) * 1963-06-27 1966-08-16 Indiana University Foundation Stannous fluorozirconate
US3594116A (en) * 1968-11-22 1971-07-20 Ozark Mahoning Co Ditin(ii)zirconium(iv)octafluoride or trifluorozirconium pentafluorostannite
FR2330127A1 (fr) * 1975-10-30 1977-05-27 Anvar Nouveaux conducteurs anioniques fluores
US4707224A (en) * 1986-10-30 1987-11-17 The Dow Chemical Company Device and method for fluorinating compounds
US4851303A (en) * 1986-11-26 1989-07-25 Sri-International Solid compositions for fuel cells, sensors and catalysts

Also Published As

Publication number Publication date
US5320917A (en) 1994-06-14
JPH04238815A (ja) 1992-08-26
CA2058875A1 (en) 1992-07-15
EP0496221A3 (en) 1992-09-09

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